Global threats of extractive industries to vertebrate biodiversity.

Mining is a key driver of land-use change and environmental degradation globally, with the variety of mineral extraction methods used impacting biodiversity across scales. We use IUCN Red List threat assessments of all vertebrates to quantify the current biodiversity threat from mineral extraction, map the global hotspots of threatened biodiversity, and investigate the links between species' habitat use and life-history traits and threat from mineral extraction. Nearly 8% (4,642) of vertebrates are assessed as threatened by mineral extraction, especially mining and quarrying, with fish at particularly high risk. The hotspots of mineral extraction-induced threat are pantropical, as well as a large proportion of regional diversity threatened in northern South America, West Africa, and the Arctic. Species using freshwater habitats are particularly at risk, while the effects of other ecological traits vary between taxa. As the industry expands, it is vital that mineral resources in vulnerable biodiversity regions are managed in accordance with sustainable development goals.

Multiscale Water Dynamics on Protein Surfaces: Protein-Specific Response to Surface Ions.

Proteins function in crowded aqueous environments, interacting with a diverse range of compounds, and among them, dissolved ions. These interactions are water-mediated. In the present study, we combine field-dependent NMR relaxation (NMRD) and theory to probe water dynamics on the surface of proteins in concentrated aqueous solutions of hen egg-white lysozyme (LZM) and bovine serum albumin (BSA). The experiments reveal that the presence of salts (NaCl or NaI) leads to an opposite ion-specific response for the two proteins: an addition of salt to LZM solutions increases water relaxation rates with respect to the salt-free case, while for BSA solutions, a decrease is observed. The magnitude of the change depends on the ion identity. The developed model accounts for the non-Lorentzian shape of the NMRD profiles and reproduces the experimental data over four decades in Larmor frequency (10 kHz to 110 MHz). It is applicable up to high protein concentrations. The model incorporates the observed ion-specific effects via changes in the protein surface roughness, represented by the surface fractal dimension, and the accompanying changes in the surface water residence times. The response is protein-specific, linked to geometrical aspects of the individual protein surfaces, and goes beyond protein-independent Hofmeister-style ordering of ions.

Ultraviolet Imaging with Low Cost Smartphone Sensors: Development and Application of a Raspberry Pi-Based UV Camera.

Here, we report, for what we believe to be the first time, on the modification of a low cost sensor, designed for the smartphone camera market, to develop an ultraviolet (UV) camera system. This was achieved via adaptation of Raspberry Pi cameras, which are based on back-illuminated complementary metal-oxide semiconductor (CMOS) sensors, and we demonstrated the utility of these devices for applications at wavelengths as low as 310 nm, by remotely sensing power station smokestack emissions in this spectral region. Given the very low cost of these units, ≈ USD 25, they are suitable for widespread proliferation in a variety of UV imaging applications, e.g., in atmospheric science, volcanology, forensics and surface smoothness measurements.

Meteorological effects of the solar eclipse of 20 March 2015: analysis of UK Met Office automatic weather station data and comparison with automatic weather station data from the Faroes and Iceland.

Here, we analyse high-frequency (1 min) surface air temperature, mean sea-level pressure (MSLP), wind speed and direction and cloud-cover data acquired during the solar eclipse of 20 March 2015 from 76 UK Met Office weather stations, and compare the results with those from 30 weather stations in the Faroe Islands and 148 stations in Iceland. There was a statistically significant mean UK temperature drop of 0.83±0.63°C, which occurred over 39 min on average, and the minimum temperature lagged the peak of the eclipse by about 10 min. For a subset of 14 (16) relatively clear (cloudy) stations, the mean temperature drop was 0.91±0.78 (0.31±0.40)°C but the mean temperature drops for relatively calm and windy stations were almost identical. Mean wind speed dropped significantly by 9% on average during the first half of the eclipse. There was no discernible effect of the eclipse on the wind-direction or MSLP time series, and therefore we can discount any localized eclipse cyclone effect over Britain during this event. Similar changes in air temperature and wind speed are observed for Iceland, where conditions were generally clearer, but here too there was no evidence of an eclipse cyclone; in the Faroes, there was a much more muted meteorological signature.This article is part of the themed issue 'Atmospheric effects of solar eclipses stimulated by the 2015 UK eclipse'.

In Vitro Longitudinal Relaxivity Profile of Gd(ABE-DTTA), an Investigational Magnetic Resonance Imaging Contrast Agent.

PURPOSE: MRI contrast agents (CA) whose contrast enhancement remains relatively high even at the higher end of the magnetic field strength range would be desirable. The purpose of this work was to demonstrate such a desired magnetic field dependency of the longitudinal relaxivity for an experimental MRI CA, Gd(ABE-DTTA). MATERIALS AND METHODS: The relaxivity of 0.5mM and 1mM Gd(ABE-DTTA) was measured by Nuclear Magnetic Relaxation Dispersion (NMRD) in the range of 0.0002 to 1T. Two MRI and five NMR instruments were used to cover the range between 1.5 to 20T. Parallel measurement of a Gd-DTPA sample was performed throughout as reference. All measurements were carried out at 37°C and pH 7.4. RESULTS: The relaxivity values of 0.5mM and 1mM Gd(ABE-DTTA) measured at 1.5, 3, and 7T, within the presently clinically relevant magnetic field range, were 15.3, 11.8, 12.4 s-1mM-1 and 18.1, 16.7, and 13.5 s-1mM-1, respectively. The control 4 mM Gd-DTPA relaxivities at the same magnetic fields were 3.6, 3.3, and 3.0 s-1mM-1, respectively. CONCLUSIONS: The longitudinal relaxivity of Gd(ABE-DTTA) measured within the presently clinically relevant field range is three to five times higher than that of most commercially available agents. Thus, Gd(ABE-DTTA) could be a practical choice at any field strength currently used in clinical imaging including those at the higher end.

Multifunctional Electroactive Nanocomposites Based on Piezoelectric Boron Nitride Nanotubes.

Space exploration missions require sensors and devices capable of stable operation in harsh environments such as those that include high thermal fluctuation, atomic oxygen, and high-energy ionizing radiation. However, conventional or state-of-the-art electroactive materials like lead zirconate titanate, poly(vinylidene fluoride), and carbon nanotube (CNT)-doped polyimides have limitations on use in those extreme applications. Theoretical studies have shown that boron nitride nanotubes (BNNTs) have strength-to-weight ratios comparable to those of CNTs, excellent high-temperature stability (to 800 °C in air), large electroactive characteristics, and excellent neutron radiation shielding capability. In this study, we demonstrated the experimental electroactive characteristics of BNNTs in novel multifunctional electroactive nanocomposites. Upon application of an external electric field, the 2 wt % BNNT/polyimide composite was found to exhibit electroactive strain composed of a superposition of linear piezoelectric and nonlinear electrostrictive components. When the BNNTs were aligned by stretching the 2 wt % BNNT/polyimide composite, electroactive characteristics increased by about 460% compared to the nonstretched sample. An all-nanotube actuator consisting of a BNNT buckypaper layer between two single-walled carbon nanotube buckypaper electrode layers was found to have much larger electroactive properties. The additional neutron radiation shielding properties and ultraviolet/visible/near-infrared optical properties of the BNNT composites make them excellent candidates for use in the extreme environments of space missions.

Surfactant-free Gd(3+)-ion-containing carbon nanotube MRI contrast agents for stem cell labeling.

There is an ever increasing interest in developing new stem cell therapies. However, imaging and tracking stem cells in vivo after transplantation remains a serious challenge. In this work, we report new, functionalized and high-performance Gd(3+)-ion-containing ultra-short carbon nanotube (US-tube) MRI contrast agent (CA) materials which are highly-water-dispersible (ca. 35 mg ml(-1)) without the need of a surfactant. The new materials have extremely high T1-weighted relaxivities of 90 (mM s)(-1) per Gd(3+) ion at 1.5 T at room temperature and have been used to safely label porcine bone-marrow-derived mesenchymal stem cells for MR imaging. The labeled cells display excellent image contrast in phantom imaging experiments, and TEM images of the labeled cells, in general, reveal small clusters of the CA material located within the cytoplasm with 10(9) Gd(3+) ions per cell.

Protein MRI contrast agent with unprecedented metal selectivity and sensitivity for liver cancer imaging.

With available MRI techniques, primary and metastatic liver cancers that are associated with high mortality rates and poor treatment responses are only diagnosed at late stages, due to the lack of highly sensitive contrast agents without Gd(3+) toxicity. We have developed a protein contrast agent (ProCA32) that exhibits high stability for Gd(3+) and a 10(11)-fold greater selectivity for Gd(3+) over Zn(2+) compared with existing contrast agents. ProCA32, modified from parvalbumin, possesses high relaxivities (r1/r2: 66.8 mmol(-1)⋅s(-1)/89.2 mmol(-1)⋅s(-1) per particle). Using T1- and T2-weighted, as well as T2/T1 ratio imaging, we have achieved, for the first time (to our knowledge), robust MRI detection of early liver metastases as small as ∼0.24 mm in diameter, much smaller than the current detection limit of 10-20 mm. Furthermore, ProCA32 exhibits appropriate in vivo preference for liver sinusoidal spaces and pharmacokinetics for high-quality imaging. ProCA32 will be invaluable for noninvasive early detection of primary and metastatic liver cancers as well as for monitoring treatment and guiding therapeutic interventions, including drug delivery.

Enhanced MRI relaxivity of aquated Gd3+ ions by carboxyphenylated water-dispersed graphene nanoribbons.

The present study demonstrates that highly water-dispersed graphene nanoribbons dispersed by carboxyphenylated substituents and conjugated to aquated Gd(3+) ions can serve as a high-performance contrast agent (CA) for applications in T1- and T2-weighted magnetic resonance imaging (MRI) with relaxivity (r1,2) values outperforming currently-available clinical CAs by up to 16 times for r1 and 21 times for r2.

Translational dynamics of water at the phospholipid interface.

The residual water-proton magnetic relaxation dispersion profile obtained from suspensions of phospholipid vesicles in deuterium oxide was found to be a logarithmic function of the proton Larmor frequency at high magnetic field strengths, and independent of Larmor frequency at low magnetic field strengths. The residual proton relaxation is caused by dipole-dipole coupling between the residual water proton in otherwise deuterated water and the phospholipid protons. The logarithmic dependence on magnetic field strength is the signature of water-proton diffusive exploration on the interface that is approximately two-dimensionally constrained. Application of relaxation theory for two-dimensional diffusion to the spin-lattice relaxation data yields a translational correlation time of approximately 70 ps for water diffusing in the interface of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) vesicles.

The magnetic field dependence of water T1 in tissues.

The magnetic field dependence of the composite (1)H(2)O nuclear magnetic resonance signal T(1) was measured for excised samples of rat liver, muscle, and kidney over the field range from 0.7 to 7 T (35-300 MHz) with a nuclear magnetic resonance spectrometer using sample-shuttle methods. Based on extensive measurements on simpler component systems, the magnetic field dependence of T(1) of all tissues studied are readily fitted at Larmor frequencies above 1 MHz with a simple relaxation equation consisting of three contributions: a power law, A*ω(-0.60) related to the interaction of water with long-lived-protein binding sites, a logarithmic term B*τ(d) *log(1+1/(ωτ(d))(2)) related to water diffusion at macromolecular interfacial regions, and a constant term associated with the high frequency limit of water-spin-lattice relaxation. The parameters A and B include the concentration and surface area dependences respectively. The logarithmic diffusion term becomes significant at high magnetic fields and is consistent with rapid translational dynamics at macromolecular surfaces. The data are fitted well with translational correlation times of approximately 15 ps for human brain white matter, but with a B value three times larger than gray matter tissues. This analysis suggests that the water-surface translational correlation time is approximately three times longer than in gray matter.

Extreme-values statistics and dynamics of water at protein interfaces.

Immobilized proteins present a unique interface with water. The water translational diffusive motions affect the high-frequency dynamics and the nuclear spin-lattice relaxation as with all surfaces; however, rare binding sites for water in protein systems add very low-frequency components to the dynamics spectrum. Water binding sites in protein systems are not identical, thus distributions of free energies and consequent dynamics are expected. (2)H(2)O spin-lattice relaxation rate measurements as a function of magnetic field strength characterize the local rotational fluctuations for protein-bound water molecules. The measurements are sensitive to dynamics down to the kilohertz range. To account for the data, we show that the extreme-values statistics of rare events, i.e., water dynamics in rare binding sites, implies an exponential distribution of activation energies for the strongest binding events. In turn, for an activated dynamical process, the exponential energy distribution leads to a Pareto distribution for the reorientational correlation times and a power law in the Larmor frequency for the (2)H(2)O spin-lattice relaxation rate constants at low field strengths. The most strongly held water molecules escape from rare binding sites in times on the order of microseconds, which interrupts the intramolecular correlations and causes a plateau in the spin-lattice relaxation rate at very low magnetic field strengths. We examine the magnetic relaxation dispersion (MRD) data using two simple but related models: a protein-bound environment for water characterized by a single potential well and a protein-bound environment characterized by a double potential well where the potential functions for the local motions of the bound-state water are of different depth. This analysis is applied to D(2)O deuterium spin-lattice relaxation on cross-linked albumin and lysozyme, which is dominated by the intramolecular relaxation driven by the dynamical modulation of the nuclear electric quadrupole coupling. We also separate the intramolecular from the intermolecular contribution to water proton spin-lattice relaxation by isotope dilution and show that the intramolecular proton data map onto the deuterium relaxation by a scale factor implied by the relative strength of the quadrupole and dipolar couplings. The temperature and pH dependence of the magnetic relaxation dispersion are complex and accounted for by changing only the weighting factors in a superposition of contributions from single-well and double-well contributions. These experiments show that the reorientational dynamics spectrum for water, in and on a protein, is characterized by a strongly asymmetric distribution with a long-time tail that extends at least to microseconds.

Water-proton-spin-lattice-relaxation dispersion of paramagnetic protein solutions.

The paramagnetic contributions to water-proton-spin-lattice relaxation rate constants in protein systems spin-labeled with nitroxide radicals were re-examined. As noted by others, the strength of the dipolar coupling between water protons and the protein-bound nitroxide radical often appears to be larger than physically reasonable when the relaxation is assumed to be controlled by 3-dimensional diffusive processes in the vicinity of the spin label. We examine the effects of the surface in biasing the diffusive exploration of the radical region and derive a relaxation model that incorporates 2-dimensional dynamics at the interfacial layer. However, we find that the local 2-dimensional dynamics changes the shape of the relaxation dispersion profile but does not necessarily reproduce the low-field relaxation efficiency found by experiment. We examine the contributions of long-range dipolar couplings between the paramagnetic center and protein-bound-water molecules and find that the contributions from these several long range couplings may be competitive with translational contributions because the correlation time for global rotation of the protein is approximately 1000 times longer than that for the diffusive motion of water at the interfacial region. As a result the electron-proton dipolar coupling to rare protein-bound-water-molecule protons may be significant for protein systems that accommodate long-lived-water molecules. Although the estimate of local diffusion coefficients is not seriously compromised because it derives from the Larmor frequency dependence, these several contributions confound efforts to fit relaxation data quantitatively with unique models.

Water and backbone dynamics in a hydrated protein.

Rotational immobilization of proteins permits characterization of the internal peptide and water molecule dynamics by magnetic relaxation dispersion spectroscopy. Using different experimental approaches, we have extended measurements of the magnetic field dependence of the proton-spin-lattice-relaxation rate by one decade from 0.01 to 300 MHz for (1)H and showed that the underlying dynamics driving the protein (1)H spin-lattice relaxation is preserved over 4.5 decades in frequency. This extension is critical to understanding the role of (1)H(2)O in the total proton-spin-relaxation process. The fact that the protein-proton-relaxation-dispersion profile is a power law in frequency with constant coefficient and exponent over nearly 5 decades indicates that the characteristics of the native protein structural fluctuations that cause proton nuclear spin-lattice relaxation are remarkably constant over this wide frequency and length-scale interval. Comparison of protein-proton-spin-lattice-relaxation rate constants in protein gels equilibrated with (2)H(2)O rather than (1)H(2)O shows that water protons make an important contribution to the total spin-lattice relaxation in the middle of this frequency range for hydrated proteins because of water molecule dynamics in the time range of tens of ns. This water contribution is with the motion of relatively rare, long-lived, and perhaps buried water molecules constrained by the confinement. The presence of water molecule reorientational dynamics in the tens of ns range that are sufficient to affect the spin-lattice relaxation driven by (1)H dipole-dipole fluctuations should make the local dielectric properties in the protein frequency dependent in a regime relevant to catalytically important kinetic barriers to conformational rearrangements.

Dimensionality of diffusive exploration at the protein interface in solution.

The dynamics of water are critically important to the energies of interaction between proteins and substrates and determine the efficiency of transport at the interface. The magnetic field dependence of the nuclear spin-lattice relaxation rate constant 1/T(1) of water protons provides a direct characterization of water diffusional dynamics at the protein interface. We find that the surface-average translational correlation time is 30-40 ps and the magnetic field dependence of the water proton 1/T(1) is characteristic of two-dimensional diffusion of water in the protein interfacial region. The reduced dimensionality substantially increases the intermolecular re-encounter probability and the efficiency of the surface exploration by the small molecule, water in this case. We propose a comprehensive theory of the translational effects of a small diffusing particle confined in the vicinity of a spherical macromolecule as a function of the relative size of the two particles. We show that the change in the apparent dimensionality of the diffusive exploration is a general result of the small diffusing particle encountering a much larger particle that presents a diffusion barrier. Examination of the effects of the size of the confinement relative to the macromolecule size reveals that the reduced dimensionality characterizing the small-molecule diffusion persists to remarkably small radius ratios. The experimental results on several different proteins in solution support the proposed theoretical model, which may be generalized to other small-particle-large-body systems like vesicles and micelles.

Water molecule contributions to proton spin-lattice relaxation in rotationally immobilized proteins.

Spin-lattice relaxation rates of protein and water protons in dry and hydrated immobilized bovine serum albumin were measured in the range of (1)H Larmor frequency from 10 kHz to 30 MHz at temperatures from 154 to 302 K. The water proton spin-lattice relaxation reports on that of protein protons, which causes the characteristic power law dependence on the magnetic field strength. Isotope substitution of deuterium for hydrogen in water and studies at different temperatures expose three classes of water molecule dynamics that contribute to the spin-lattice relaxation dispersion profile. At 185 K, a water (1)H relaxation contribution derives from reorientation of protein-bound molecules that are dynamically uncoupled from the protein backbone and is characterized by a Lorentzian function. Bound-water-molecule motions that can be dynamically uncoupled or coupled to the protein fluctuations make dominant contributions at higher temperatures as well. Surface water translational diffusion that is magnetically two-dimensional makes relaxation contributions at frequencies above 10 MHz. It is shown using isotope substitution that the exponent of the power law of the water signal in hydrated immobilized protein systems is the same as that for protons in lyophilized proteins over four orders of magnitude in the Larmor frequency, which implies that changes in the protein structure associated with hydration do not affect the (1)H spin relaxation.

A multi-scale remote sensing approach for monitoring northern peatland hydrology: present possibilities and future challenges.

Remote sensing has the potential to provide quantitative spatially explicit hydrological information across northern peatland complexes. This paper details a multi-scale remote sensing approach for assessing the use of Sphagnum mosses as proxy indicators of near-surface hydrology. Several spectral indices developed from the near infra-red (NIR) and shortwave infra-red (SWIR) liquid water absorption bands, as well as a biophysical index can be correlated with measures of near-surface moisture in the laboratory, in the field and from airborne imagery. Data from all platforms revealed similar patterns in the spectral indices in relation to changes in moisture although the strength of correlations was reduced as the spatial scale increased. The rapid collection of temporally and spatially explicit hydrological data means that the technique has potential practical application for environmental managers and peatland scientists at the local scale. The task of up-scaling the technique for use in operational peatland hydrological monitoring to the global scale is challenging but achievable, and requires further investigation into the heterogeneity of near-surface moisture across Sphagnum patches and the application of novel image processing techniques to improve the spatial resolution of currently available satellite imagery.

Comparison of Low Cost Miniature Spectrometers for Volcanic SO(2) Emission Measurements.

Miniature ultraviolet USB coupled spectrometers have become ubiquitously applied over the last decade for making volcanic SO(2) emission rate measurements. The dominantly applied unit has recently been discontinued however, raising the question of which currently available devices should now be implemented. In this paper, we consider, and make recommendations on this matter, by studying a number of inexpensive compact spectrometers in respect of measurement performance and thermal behaviour. Of the studied units, the Avaspec demonstrated the best prospects for the highest time resolution applications, but in the majority of cases, we anticipate users likely preferring the less bulky USB2000+s.

Spin-diffusion couples proton relaxation rates for proteins in exchange with a membrane interface.

Changes in nuclear spin-lattice relaxation rates that are induced by a freely diffusing paramagnetic relaxation agent are examined for a protein in solution and compared to the case where the protein binds to a membrane. In the solution case, the intramolecular cross-relaxation rates are modest and large differences are observed in the oxygen induced protein-proton relaxation rates. In the case where a dynamic equilibrium between solution and membrane-bound environments is established, the intramolecular (1)H cross-relaxation rates for the protein protons increase dramatically because of the slow reorientational motion in the membrane-bound environment. As a consequence, all protein protons relax with nearly the same spin-lattice relaxation rate constants when bound to the membrane, and site specific relaxation effects of the diffusing paramagnet are suppressed. Slowly reorienting sites or rotationally immobilized sites sampled by observable molecules in vivo will demonstrate similar relaxation leveling effects.